1-alkoxy-1-azolylmethyloxiranes and the use thereof as crop protection agents

ABSTRACT

1-Alkoxy-1-azolylmethyloxiranes of the general ##STR1## where R 1  and R 2  are identical or different and each is C 1  -C 8  -alkyl, C 3  -C 8  -cycloalkyl, C 5  -C 8  -cycloalkenyl, tetrahydropyranyl, norbornyl, pyridyl, naphthyl, biphenylyl or phenyl, each of which is unsubstituted or mono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl of 1 to 4 carbon atoms in each case, R 3  is C 1  -C 4  -alkyl, X is CH or N, the acid addition salts and metal complexes thereof which are tolerated by plants, processes for their manufacture, and their use for combating fungi.

This application is a continuation of application Ser. No. 07/492,806,filed on Mar. 13, 1990, now abandoned.

The present invention relates to novel azole compounds, the preparationthereof and fungicides containing these, and methods for combatingfungi.

The use ofcis-2-(1,2,4-triazol-1-ylmethyl)-2-tert-butyl-3-(4-chlorophenyl)oxiraneas a fungicide has been disclosed (DE-A 3218130). However, thefungicidal action is unsatisfactory in some cases.

We have now found that 1-alkoxy-1-azolylmethyloxiranes of the formula I##STR2## where R¹ and R² are identical or different and each is C₁ -C₈-alkyl, C₃ -C₈ -cycloalkyl, C₅ -C₈ -cycloalkenyl, tetrahydropyranyl,norbornyl, pyridyl, naphthyl, biphenylyl or phenyl, each of which can besubstituted once to three times by halogen, nitro, phenoxy, amino,alkyl, alkoxy or haloalkyl of 1 to 4 carbons in each case, R³ is C₁ -C₄-alkyl, X is CH or N, and the acid addition salts and metal complexesthereof which are tolerated by plants, have a better fungicidal actionthan known azole compounds.

The compounds of the formula I contain asymmetric carbons and cantherefore exist as enantiomers and diastereomers. Mixtures ofdiastereomers of the compounds according to the invention can beseparated in a conventional manner, for example on the basis of theirdifferent solubilities or by column chromatography, and the purediastereomers can be isolated. Racemates of the compounds according tothe invention can be resolved by conventional methods, for example byformation of a salt with an optically active acid, separation of thediastereomeric salts and liberation of the enantiomers with a base. Itis possible to use both the pure diastereomers or enantiomers and themixtures thereof produced in the synthesis as fungicidal agents.

Examples of R¹ and R² are C₁ -C₄ -alkyl, methyl, ethyl, isopropyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl,1-naphthyl, 2-naphthyl, p-biphenylyl, phenyl, 2-chlorophenyl,2-fluorophenyl, 2-bromophenyl, 3-chlorophenyl, 3-bromophenyl,3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl,2,4-dichlorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophenyl,2,6-dichlorophenyl, 3-chloro-6-fluorophenyl, 2-methoxyphenyl,3-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 4-ethylphenyl,4-isopropylphenyl, 4-tert-butylphenyl, 4-tert-butyloxyphenyl,2-chloro-4-fluorophenyl, 2-chloro-6-fluorophenyl,2-chloro-6-methylphenyl, 3,4-dimethoxyphenyl, 3-phenoxyphenyl,4-phenoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 3-aminophenyl,4-aminophenyl, 2-aminophenyl, 2-trifluoromethylphenyl,3-trifluoromethylphenyl, 4-trifluoromethylphenyl,4-phenylsulfonylphenyl, 3-pyridyl, tetrahydropyranyl, cyclopropyl,cyclopentyl, cyclohexyl, 2-cyclohexenyl, 3-cyclohexenyl and norbornyl.

Examples of acid addition salts are the hydrochlorides, bromides,sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates.The activity of the salt derives from the cation so that the nature ofthe anion is generally immaterial. The salts of the active ingredientaccording to the invention are prepared by reacting the1-alkoxy-1-azolylmethyloxiranes I with suitable acids.

Metal complexes of the active ingredients I or salts thereof can beformed with metals such as copper, zinc, tin, manganese, iron, cobalt ornickel, by reacting the 1-alkoxy-1-azolylmethyloxiranes withcorresponding salts, e.g. the chlorides or sulfates such as zincchloride, copper sulfate, tin chloride, manganese sulfate or ironsulfate.

The compounds of the formula I can be prepared by, for example, reactinga compound of the formula II ##STR3## where R¹ and R² have the statedmeanings, with a compound of the formula III ##STR4## where Me ishydrogen or a metal (e.g. Na or K) and X has the stated meaning, in thepresence of a thionyl halide and of an alcohol of the formula IV

    R.sup.3 OH                                                 IV

where R³ has the abovementioned meaning.

The reaction is carried out in the presence or absence of a solvent ordiluent, generally at from -30° to 80° C. The preferred solvents anddiluents include nitriles such as acetonitrile or propionitrile, etherssuch as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane orisopropyl ether and, in particular, hydrocarbons and chlorohydrocarbonssuch as pentane, hexane, toluene, methylene chloride, chloroform, carbontetrachloride, dichloroethane or mixtures thereof.

The novel starting compounds II are obtained, for example, byepoxidation of the corresponding olefins V ##STR5## where R¹ and R² havethe abovementioned meanings, with peroxycarboxylic acids such asperbenzoic acid, 3-chloroperbenzoic acid, 4-nitroperbenzoic acid,monoperphthalic acid, peracetic acid, perpropionic acid, permaleic acid,monopersuccinic acid, perpelargonic acid or trifluoroperacetic acid ininert solvents, preferably chlorinated hydrocarbons, e.g. methylenechloride, chloroform, carbon tetrachloride or dichloroethane, or inorganic acids such as acetic acid, in esters such as ethyl acetate, inketones such as acetone or in amides such as dimethylformamide, in thepresence or absence of a buffer such as sodium acetate, sodiumcarbonate, disodium hydrogen phosphate or ethylenediaminetetraaceticacid. The reaction is generally carried out at from 10° to 100° C. andcan be catalyzed with, for example, iodine, sodium tungstate or light.Also suitable for the oxidation are alkaline solutions of hydrogenperoxide (e.g. 20 to 50% by weight, preferably 25 to 35% by weight) inalcohols such as methanol or ethanol, ketones such as acetone, ornitriles such as acetonitrile, generally at from 10° to 50° C.,preferably 20° to 35° C., in particular 25° to 30° C., and alkylhydroperoxides, e.g. tert-butyl hydroperoxide, with the addition of acatalyst, e.g. sodium tungstate, pertungstic acid, molybdenumhexacarbonyl or vanadyl acetylacetonate. Some of the said oxidizingagents can be generated in situ.

The compounds V can be prepared by conventional processes forsynthesizing aldehydes (cf., for example, Houben-Weyl-Muller, Methodender Organischen Chemie, Georg Thieme Verlag, Stuttgart 1983, Vol. E 3).

The Examples which follow illustrate the preparation of the activeingredients.

I. PREPARATION OF THE STARTING MATERIALS EXAMPLE A Preparation ofE/Z-2-(4-fluorophenyl)-3-phenylpropenal

4.2 g of sodium hydroxide in 30 ml of water are added to a solution of26.5 g of benzaldehyde in 300 ml of methanol. The reaction mixture iscooled to 10° C., and 36 g of 4-fluorophenylacetaldehyde are rapidlyadded, during which the solution rises to 30°-40° C. The reactionsolution is stirred at 40° C. for 10 hours and then cooled and thecrystals which have separated out are filtered off with suction. 31.6 g(56%) of E/Z-2-(4-fluorophenyl)-3-phenylpropenal of melting point87°-94° C. are obtained.

EXAMPLE B Preparation of cis-2-formyl-2-(4-fluorophenyl)-3-phenyloxirane

67.8 g of E/Z-2-(4-fluorophenyl)-3-phenylpropenal are dissolved in 300ml of methanol, and 1 ml of concentrated sodium hydroxide solution isadded. The reaction solution is stirred at 0° C. while 20.5 g ofhydrogen peroxide (about 50% by weight) are slowly added dropwise notallowing the internal temperature to exceed 30° C. After the addition iscomplete, the mixture is stirred at room temperature for 6 hours, then100 ml of water are added, and the resulting emulsion is extracted byshaking with methyl tert-butyl ether. The isolated organic phase is thendried over sodium sulfate and concentrated. 55.9 g (77%) ofcis-2-formyl-2-(4-fluorophenyl)-3-phenyloxirane are obtained.

II. PREPARATION OF THE FINAL PRODUCTS EXAMPLE 1

7.4 g of thionyl chloride are added to a solution of 17.5 g of triazolein 75 ml of methylene chloride at 0° C. and under a nitrogen atmosphere.After the addition is complete, the mixture is stirred at roomtemperature for 30 minutes and then 2 g of methanol and 10 g ofcis-2-formyl-2-(4-fluorophenyl)-3-phenyloxirane are added. The reactionmixture is stirred at room temperature for 12-15 hours and then 100 mlof water are added to the solution, and the organic phase is separatedoff. The remaining aqueous phase is extracted by shaking twice withmethylene chloride, and the collected organic phases are washed twicewith saturated sodium bicarbonate solution. The isolated organic phaseis then dried over sodium sulfate and concentrated, and the residue ispurified by flash chromatography on silica gel (9:1 ethylacetate/n-hexane). 2.3 g (18%) of1'RS-cis-2-[1-(1,2,4-triazol-1-yl)-1-methoxymethyl]-2-(4-fluorophenyl)-3-phenyloxiraneare obtained as a 5:1 diastereomer mixture, melting point 135°-138° C.

The compounds listed in the Table can be prepared as in Example 1.

                                      TABLE                                       __________________________________________________________________________     ##STR6##                                                                                                            I                                      Ex.                                                                           No.                                                                              R.sup.1 R.sup.2  R.sup.3                                                                            X  m.p./IR                                                                             Isomer                                      __________________________________________________________________________     1 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        CH.sub.3                                                                           N  135-138° C.                                                                  D.sub.1 :D.sub.2 = 5:1                       2 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        CH.sub.3                                                                           CH resin D.sub.1 :D.sub.2 = 4:1                       3 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        C.sub.2 H.sub.5                                                                    N                                                     4 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                     5 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           CH                                                    6 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    C.sub.2 H.sub.5                                                                    N                                                     7 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    C.sub.3 H.sub.7                                                                    N                                                     8 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    iso-C.sub.3 H.sub.7                                                                N                                                     9 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    C.sub.4 H.sub.9                                                                    N                                                    10 4-FC.sub.6 H.sub.4                                                                    3-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    11 4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    12 4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    C.sub.2 H.sub.5                                                                    N                                                    13 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            CH.sub.3                                                                           N                                                    14 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            C.sub.2 H.sub.5                                                                    N                                                    15 4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                CH.sub.3                                                                           N                                                    16 4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              CH.sub.3                                                                           N                                                    17 4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              CH.sub.3                                                                           CH                                                   18 4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              C.sub.2 H.sub.5                                                                    N                                                    19 4-FC.sub.6 H.sub. 4                                                                   4-CF.sub.3C.sub.6 H.sub.4                                                              CH.sub.3                                                                           N                                                    20 4-FC.sub.6 H.sub.4                                                                    4-CF.sub.3C.sub.6 H.sub.4                                                              C.sub.2 H.sub.5                                                                    N                                                    21 4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    22 4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     C.sub.2 H.sub.5                                                                    N                                                    23 4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    24 4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     C.sub.3 H.sub.7                                                                    N                                                    25 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             CH.sub.3                                                                           N                                                    26 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             CH.sub.3                                                                           N                                                    27 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             CH.sub.3                                                                           N                                                    28 4-FC.sub.6 H.sub.4                                                                     ##STR7##                                                                              CH.sub.3                                                                           N                                                    29 4-FC.sub.6 H.sub.4                                                                    4-NO.sub.2C.sub.6 H.sub.4                                                              CH.sub.3                                                                           N                                                    30 4-FC.sub.6 H.sub.4                                                                    4-NH.sub.2C.sub.6 H.sub.4                                                              CH.sub.3                                                                           N                                                    31 4-FC.sub.6 H.sub.4                                                                    2-C.sub.10 H.sub.7                                                                     CH.sub.3                                                                           N                                                    32 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             CH.sub.3                                                                           N                                                    33 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    34 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           CH                                                   35 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    C.sub.2 H.sub.5                                                                    N                                                    36 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    C.sub.3 H.sub.7                                                                    N                                                    37 C.sub.6 H.sub.5                                                                       4-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    38 C.sub.6 H.sub.5                                                                       4-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           CH                                                   39 C.sub.6 H.sub.5                                                                       2,4-Cl.sub.2C.sub.6 H.sub.3                                                            CH.sub.3                                                                           N                                                    40 C.sub.6 H.sub.5                                                                       2-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    41 C.sub.6 H.sub.5                                                                       4-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    42 C.sub.6 H.sub.5                                                                       2-CF.sub.3C.sub.6 H.sub.4                                                              CH.sub.3                                                                           N                                                    43 C.sub.6 H.sub.5                                                                       2-OCH.sub.3C.sub.6 H.sub.4                                                             CH.sub.3                                                                           N                                                    44 2-ClC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    45 2-ClC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    46 2-ClC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    47 2-Cl C.sub.6 H.sub.4                                                                  4-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    48 4-ClC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    49 4-ClC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           CH                                                   50 4-ClC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    51 4-ClC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    52 4-ClC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    53 4-ClC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                              CH.sub.3                                                                           N                                                    54 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    55 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2,4-Cl.sub.2C.sub.6 H.sub.3                                                            CH.sub.3                                                                           N                                                    56 4-BrC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    57 cyclohexyl                                                                            2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    58 cyclohexyl                                                                            4-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    59 cyclohexyl                                                                            2-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    60 cyclohexyl                                                                            4-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    61 cyclohexyl                                                                            4-ClC.sub.6 H.sub.4                                                                    C.sub.2 H.sub.5                                                                    N                                                    62 cyclohexyl                                                                            4-ClC.sub.6 H.sub. 4                                                                   C.sub.3 H.sub.7                                                                    N                                                    63 cyclohexyl                                                                            2,4-Cl.sub.2C.sub.6 H.sub.3                                                            CH.sub.3                                                                           N                                                    64 cyclohexyl                                                                            2,4-Cl.sub.2C.sub.6 H.sub.3                                                            CH.sub.3                                                                           CH                                                   65                                                                                ##STR8##                                                                             2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    66                                                                                ##STR9##                                                                             4-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    67 CH.sub.3                                                                              2-ClC.sub.6 H.sub.4                                                                    CH.sub.3                                                                           N                                                    68 CH.sub.3                                                                              4-FC.sub.6 H.sub.4                                                                     CH.sub.3                                                                           N                                                    69 4-FC.sub.6 H.sub.4                                                                    3-pyridyl                                                                              CH.sub.3                                                                           N                                                    70 4-FC.sub.6 H.sub.4                                                                    norbornyl                                                                              CH.sub.3                                                                           N                                                    71 4-FC.sub.6 H.sub.4                                                                    p-C.sub.12 H.sub.9                                                                     CH.sub.3                                                                           N                                                    72 4-FC.sub.6 H.sub.4                                                                    3-cyclohexenyl                                                                         CH.sub.3                                                                           N                                                    73 4-FC.sub.6 H.sub.4                                                                    2-cyclohexenyl                                                                         CH.sub.3                                                                           N                                                    __________________________________________________________________________

Generally speaking, the novel compounds are extremely effective on abroad spectrum of phytopathogenic fungi, in particular those from theAscomycetes and Basidiomycetes classes. Some of them have a systemicaction and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in vegetables and fruit.

The compounds are applied by spraying or dusting the plants with theactive ingredients, or treating the seeds of the plants with the activeingredients. They may be applied before or after infection of the plantsor seeds by the fungi.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin, sulfitewaste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient. The application rates arefrom 0.02 to 3 kg or more of active ingredient per hectare, depending onthe type of effect desired. The novel compounds may also be used forprotecting materials, for example against Paecilomyces variotii.

The agents and the ready-to-use formulations prepared from them, such assolutions, emulsions, suspensions, powders, dusts, pastes and granules,are applied in conventional manner, for example by spraying, atomizing,dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weightof N-methyl-α-pyrrolidone. A mixture is obtained which is suitable forapplication in the form of very fine drops.

II. 20 parts by weight of compound no. 2 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into water and uniformly distributing it therein, an aqueousdispersion is obtained.

III. 20 parts by weight of compound no. 2 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into water andfinely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 1 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanol, 65 parts by weight ofa mineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into water and uniformlydistributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 2 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 7 parts by weight of powdered silicagel, and triturated in a hammer mill. By uniformly distributing themixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 1 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 2 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 40 parts by weight of compound no. 1 is intimately mixed with 10parts by weight of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater to give a stable aqueous dispersion. Dilution in water gives anaqueous dispersion.

IX. 20 parts by weight of compound no. 2 is intimately mixed with 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil. A stable oilydispersion is obtained.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and fungicides, and mayfurthermore be mixed and applied together with fertilizers. Admixturewith other fungicides frequently results in an increase in thefungicidal spectrum.

USE EXAMPLES

For comparison purposes, the active ingredientcis-2-(1,2,4-triazol-1-yl-methyl)-2-(tert-butyl)-3-(4-chlorophenyl)-oxirane(A) disclosed in DE-A-3,218,150 was employed.

USE EXAMPLE 1 Action on wheat brown rust

Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dustedwith spores of brown rust (Puccinia recondita). The posts were thenplaced for 24 hours at 20° to 22° C. in a high-humidity (90-95%)chamber. During this period the spores germinated and the germ tubespenetrated the leaf tissue. The infected plants were then sprayed torunoff with aqueous liquors containing (dry basis) 80% of activeingredient and 20% of emulsifier. After the sprayed-on layer had dried,the plants were set up in the greenhouse at 20° to 22° C. and a relativehumidity of 65 to 70%. The extent of rust fungus spread on the leaveswas assessed after 8 days.

The results show that active ingredients nos. 1 and 2, applied as 0.006wt % spray liquors, had a better fungicidal action (5% attack) thanprior art active ingredient A (50% attack).

USE EXAMPLE 2 Action on Botrytis cinerea in pimientos

Pimiento seedlings of the "Neusiedler Ideal Elite" variety with 4 to 5well developed leaves were sprayed to runoff with aqueous suspensionscontaining (dry basis) 80% of active ingredient and 20% of emulsifier.After the sprayed-on layer had dried, the plants were sprayed with aconidial suspension of the fungus Botrytis cinerea and kept in ahigh-humidity chamber at 22° to 24° C. After 5 days, the disease hadspread on the untreated control plants to such an extent that thenecroses covered the major portion of the leaves.

The results show that active ingredients nos. 1 and 2, applied as 0.05wt % spray liquors, had a better fungicidal action (5% attack) thancomparative agent A (40% attack).

We claim:
 1. A 1-alkoxy-1-azolylmethyloxirane of formula I: ##STR10##wherein R¹ is 4-fluorophenyl; and R² is C₃ -C₈ -cycloalkyl, C₅ -C₈-cycloalkenyl, tetrahydropyranyl, norbornyl, naphthyl, biphenylyl orphenyl, each of which is unsubstituted or mono- to tri-substituted byhalogen, nitro, phenoxy, amino, alkyl, alkoxy or haloalkyl of 1 to 4carbon atoms in each case; and R³ is C₁ -C₄ -alkyl, and the acidaddition salts and metal complexes thereof which are tolerated byplants.
 2. A fungicidal composition containing a solid or a liquidcarrier and a fungicidally effective amount of a1-alkoxy-1-azolylmethyloxirane of the formula I ##STR11## wherein R¹ is4-fluorophenyl; R² is C₃ -C₈ -cycloalkyl, C₅ -C₈ -cycloalkenyl,tetrahydropyranyl, norbornyl, naphthyl, biphenylyl or phenyl, each ofwhich is unsubstituted or mono- to tri-substituted by halogen, nitro,phenoxy, amino, alkyl, alkoxy or haloalkyl of 1 to 4 carbon atoms ineach case, and R³ is C₁ -C₄ -alkyl, or an acid addition salt or metalcomplex thereof tolerated by plants.
 3. A process for combating fungi,comprising: applying a fungicidally effective amount of a1-alkoxy-1-azolylmethyloxirane of the formula I: ##STR12## wherein R¹ is4-fluorophenyl; R² is C₃ -C₈ -cycloalkyl, C₅ -C₈ -cycloalkenyl,tetrahydropyranyl, norbornyl, naphthyl, biphenylyl or phenyl, each ofwhich is unsubstituted or mono- to tri-substituted by halogen, nitro,phenoxy, amino, alkyl, alkoxy or haloalkyl of 1 to 4 carbon atoms ineach case, and R³ is C₁ -C₄ -alkyl, or an acid addition salt or metalcomplex thereof tolerated by plants to areas, plants or seed threatenedby fungus attack.
 4. A compound as set forth in claim 1, where R¹ is4-fluorophenyl, R² is phenyl and, R³ is methyl.
 5. The composition ofclaim 2, wherein the composition contains from 0.1 to 95 wt. % of activefungicidal ingredient.
 6. The process of claim 3, wherein from 0.02 to 3kg of fungicidally active ingredient is applied per hectare of area.